CZ289892B6 - Low-dust granules of plastic additives, process of their preparation and their use for stabilizing organic polymers - Google Patents

Abstract

In the present invention there are disclosed low-dust granules of plastic additives, comprising at least 10 percent by weight of calcium stearate, whereby the water content of the calcium stearate is less than 2 percent by weight, having a particle size distribution, in accordance with ISO 3435, of from 1 mm to 10 mm, a loose bulk density of greater than 400 g/l and a flowability in accordance with DIN 53492 of less than 15 s (tR25). In the present invention there is also claimed a process for their production, and the use of these granules for the stabilization of organic polymers.

Description

Low-dusting granules of plastic additives, process for their production and their use to stabilize organic polymers

Technical field

The invention relates to low-powder granules of plastic additives containing calcium stearate, to a process for the production of these granules and to the use of these granules to stabilize plastics.

BACKGROUND OF THE INVENTION

Organic polymers (plastics), in particular polyolefins, generally require the addition of additives to be processed and in order to maintain their properties for a long time. In addition to light and heat, the residues of the catalysts used for the preparation have a detrimental effect on organic polymers. The prior art describes a very wide variety of groups of substances which can be used as additives and stabilizers. Due to a number of processes that damage organic polymers, not all of which are explained in detail, mixtures of multiple additives are often used.

Generally, the additives are in powder form. However, additive mixtures in powder form have a number of disadvantages, such as their dustiness, even the dust explosiveness, the tendency to separate, and also the difficulty in metering. For this reason, there is a demand for commercial forms of additives that do not exhibit these disadvantages. To this end, for example, sintering processes (in the aqueous phase and optionally using dispersants), mixing with binders or compression using a pellet press are described. In most cases, however, the resulting commercial forms still do not have adequate mechanical properties. Commercial forms often also contain water or other binders which may cause problems during subsequent incorporation into the organic polymer or require special precautions. Thus, there is a need for granular mixtures of long shelf-life additives that contain no binders. Granular material of this type is also desirable and is also environmentally friendly, whose importance is increasing (low dustiness, saving material by eliminating the binder).

In this context, U.S. Pat. No. 5,240,642 discloses a process for obtaining granular forms of additives, which are organic acid and an inorganic additive of an anti-acid nature and tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, in the presence of the latter in molten form, by homogeneously distributing the material in a powdered material of an anti-acid nature, extruding the material, cooling the extruded fibers and then forming granules. Unfortunately, the granules obtained in this way are characterized by several drawbacks, namely these granules still release a considerable amount of dust, which is particularly harmful to workers in the large scale industrial process, tend to separate during storage and transport, and have metering problems.

SUMMARY OF THE INVENTION

Surprisingly, plastic additive granules that meet a wide range of industry requirements are obtained according to the invention by heating a mixture of plastic additives and calcium stearate up to at least 80% of the calcium stearate component is melted and resulting in subsequent plastic compression.

The new plastic additive granules are very uniform and are characterized by excellent bulk material properties, in particular the absence of dust, flowability and abrasion resistance, and good shelf life. They can be metered very well into the organic polymers to be

Stabilized, and exhibit thermally better melting properties than conventional calcium stearates or powdered calcium stearate mixtures.

Accordingly, in addition to the methods described in more detail below, the invention relates to low-dusting granules of plastic additives which contain at least 10 wt. calcium stearate, exhibit particle size dispersion, according to ISO 3435 (continuous mechanical handling equipment -classification and symbolization of bulk materials), from 1 to 10 mm, bulk density greater than 400 g / l, and tR25, i.e., velocity flow at a given nozzle diameter according to DIN 53492 (plastic testing, granulation plastic flotation determination), less than 15 s.

For the purposes of the present invention, the term "low-dusting granules" refers to granules whose dust release in the Heubach test is less than 0.15% by weight. (after 5 minutes). Throughout the description, the term "new granules" refers to low-dust granules as defined above. For the sake of simplicity, "plastic additives" are also referred to herein as "plastic additives".

For purposes of the invention, calcium stearate is the reaction product of commercially available mixtures of fatty acids and a calcium compound. Commercially available mixtures of fatty acids and calcium compounds. Commercially available fatty acid mixtures comprise a mixture of C14-C20 fatty acids with a predominant stearic acid content and often also palmitic acid, for example about 67% stearic acid and 33% palmitic acid. According to the invention, the calcium stearate has a low crystalline water content, i.e. it is substantially amorphous. Depending on environmental influences (e.g. storage conditions) and prior heat treatment, the total water content of the calcium stearate or calcium stearate component may vary, but is preferably less than 1% by weight.

According to a preferred embodiment, the new granules comprise at least 20% by weight, and particularly preferably at least 30% by weight. % or 100 wt. calcium stearate.

The particle size distribution of the new granules, defined according to ISO 3435, is preferably from 1 to 6 mm, particularly preferably from 2 to 6 mm.

The bulk density is preferably more than 500 g / l, but it depends on the density of the overall composition and may be higher or lower for compositions whose density differs significantly from that of calcium stearate. Thus, the values refer to mixtures in which the density does not differ by more than 10% from that of calcium stearate. If the density of the mixture varies more, the bulk density should be corrected by a factor given by the ratio between the density of the calcium stearate and the density of the mixture.

According to the invention, the flowability determined according to DIN 53942 is preferably less than 15 s (tR15), most preferably less than 10 s (tR15).

Dust release is determined by the Heubach test in an experimental setting similar to practical conditions, the test material being kept in motion to determine the tendency to scrub by dust. The device used is manufactured by Heubach Engineering GmBH, Langelsheim, Germany. The test material (sample weight is 50 g) moves at 30 revolutions per minute, corresponding to a peripheral speed of 19 cm per second, for 5 minutes in a 2.5-liter dust generating unit containing three obstructions in the direction of rotating at an angle of 45 ° to the wall of the unit, with an air flow of 0.32 L per second carrying the fine component onto the filter. According to the invention, the content of the fine component determined in this way preferably does not exceed 0.1% by weight.

Other plastic additives which may be present in the granules according to the invention are known per se, either alone or in various combinations. Many of the plastic additives described below are commercially available. Other plastic additives can be prepared by known methods and under standard conditions, and are in the form of solids (e.g., powders or granules), melts (e.g., directly from synthesis), or liquids.

-2GB 289892 B6

The invention further relates to a process for the manufacture of plastic additive granules which comprises heating a plastic additive mixture comprising at least 10 to 100 wt. calcium stearate, until at least 80% of the calcium stearate component is melted, extruding the mixture through a nozzle or aperture plate wherein the nozzle or aperture diameter is from 1 to 10 mm, and chopping the resulting extrudate in a plastic state to obtain granules. The term " plastic state " refers to fibers that have not yet solidified, fibers that are not solid, and, in terms of viscosity, generally have viscosities in the range of from 1 to 500,000 Pa.s, preferably from 1 to 100,000 Pa. .with.

The diameter of the thimble or hole is preferably from 2 to 6 mm.

The plastic additives (or calcium stearate) are preferably melted in a single or double screw extruder. These extruders are known in the plastics processing industry and are manufactured, for example, by Buss (Switzerland), Brabender (Germany), Werner und Pfleiderer (Germany) or Biihler (Germany). Plastic additives are generally used here in the form of solids (e.g. powders or granules), but it is also possible to use melt, aqueous suspensions, or, in small amounts, liquid additives. After or alternatively during the chopping of the extrudates, which takes place in a still soft state and after passing through the nozzle or perforated plate, the granule particles are cooled. The cooling may be carried out in the form of wet cooling with water (e.g. water, water film, water ring, etc.) or preferably air (e.g. air film, air vortex, etc.) or a combination of these types of cooling. If water cooling is used, subsequent dewatering and drying (preferably on a fluid bed) is required. The industrial uses of these cooling methods are known. It is essential that the granulation takes place in a plastic state before cooling, as opposed to the extrusion and milling granulation methods which are common in the industry.

The melt production of calcium stearate is usually not carried out at a single constant temperature, but instead the temperature of the material varies according to the diagram in a continuous process. Conveniently, a maximum temperature of above 140 ° C is achieved, with maximum temperatures above 150 ° C being preferred, depending on the nature of the other ingredients of the mixture, and in general maximum temperatures of up to 220 ° C are suitable. These temperatures indicate the temperature of the material.

Further preferred is a method that further comprises exhausting the gases. In carrying out the process, the gas exhaust device is preferably located in a zone in which calcium stearate is melted or in a subsequent zone.

The granules are preferably produced using an extruder, wherein a material temperature of over 130 ° C is achieved at at least one location in the extruder.

The plastic additive granules obtained by the process according to the invention are also an object of the invention. Analogously, the preferred embodiments described apply to them.

Other plastic additives that may be present in the granules of the invention are preferably compounds selected from the group consisting of sterically hindered amines (HALS), sterically hindered phenols, phosphites or phosphonites, hydrotalcites, metal oxides, metal carbonates, other metal soaps, antistatic agents, antiblocking agents, flame retardants, thioesters, internal and external lubricants, pigments, UV absorbers and other light stabilizers.

The granules may also contain other substances, such as thermoplastic polymers (e.g. polyolefins or polyolefin waxes).

A particularly preferred embodiment of the invention is a combination of calcium stearate with at least one sterically hindered phenol type antioxidant and at least one phosphite or phosphonite. Particularly preferred is furthermore a combination of calcium stearate with at least one of

Groups consisting of sterically hindered amines containing at least one 2,2,6,6-tetramethylpiperidine residue.

A particularly preferred embodiment of the invention comprises a combination of calcium stearate with at least one antioxidant of the sterically hindered phenol type and at least one phosphite or phosphonite or at least one compound of the group consisting of sterically hindered amines containing at least one 2,2,6,6-tetramethylpiperidine residue.

Sterically hindered amines, preferably piperidine compounds, are known in principle as light stabilizers. These compounds contain one or more groups of formula I

They may be relatively low molecular weight (less than 700) or relatively high molecular weight compounds. The latter may also be oligomeric or polymeric products.

Particularly important stabilizers are the following classes of tetramethylpiperidine compounds:

a) Compounds of formula II

(II) wherein n is a number from 1 to 4, preferably 1 or 2,

R ¹ represents a hydrogen atom, an oxy group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 8 carbon atoms, an alkynyl group having 3 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an alkanoyl group having 1 to 12 carbon atoms C 8 -C 3 alkenoyl, glycidyl or -CH ₂ CH (OH) -Z, wherein:

Z represents a hydrogen atom, a methyl group or a phenyl group, wherein R ¹ preferably represents a C 1 -C 4 alkyl group, an allyl group, a benzyl group, an acetyl group or an acryloyl group, and

R is, when n is 1, a hydrogen atom or one or more oxygen atoms interrupted by an alkyl group having 1 to 18 carbon atoms, a cyanethyl group, a benzyl group, a glycidyl group, a monovalent aliphatic, cycloaliphatic,

-4C 289892 B6 araliphatic, unsaturated or aromatic carboxylic acids, carbamic acids or phosphorus-containing acids or a monovalent silyl residue, preferably a C 2 -C 18 aliphatic carboxylic acid residue, C 7 -C 6 cycloaliphatic carboxylic acids, α, β-unsaturated carboxylic acids C 3 -C 5 acids or C 7 -C 15 aromatic carboxylic acids, when n is 2, R ² is C 1 -C 12 alkylene, C 4 -C 12 alkenylene, xylylene, bivalent radical an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, a dicarbamic acid or a phosphorus-containing or divalent silyl radical, preferably a C 2 -C 36 aliphatic dicarboxylic acid radical, a C 8 -C 14 cycloaliphatic or aromatic dicarboxylic acid, or an aliphatic, cycloaliphatic or aromati C 8 -C 14 dicarbamic acids, when n is 3, R ^{2 is a} trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl radical, and when n is 4, R is ^{2 a} tetravalent aliphatic, cycloaliphatic or aromatic tetracarboxylic acid residue.

Any substituents which are C 1 -C 12 alkyl are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n- nonyl, n-decyl, n-undecyl or n-dodecyl groups.

As C 1 -C 18 alkyl, R ² may, for example, be as defined above and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

When R @ ¹ represents a C3 -C8 alkenyl group, it may be, for example, 1-propenyl, allyl, methylallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2- butenyl group.

R @ ¹ as C3 -C8 alkynyl is preferably propargyl.

In the meaning of the C7 -C12 aralkyl group, R @ ¹ is, in particular, phenylethyl and especially benzyl.

R ¹ for C 1 -C 8 alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl, and for C 3 -C 5 alkenoyl, R ^{1 is} especially akiyloyl.

When R ² is a monovalent radical of a carboxylic acid is, for example, an acetyl, stearoyl, acryloyl, methacryloyl, benzoyl or β- (3,5-di-tertbutyl-4-hydroxyphenyl) propionyl.

When R ² is a divalent radical of a dicarboxylic acid is, for example malonyl, succinyl, glutaryl, adipoyíovou, suberoylovou, sebakoylovou, maleoylovou, phthaloyl, dibutylmalonylovou, dibenzylmalonylovou, butyl (3,5-tertbutyl-4-hydroxybenzyl) malonyl or bicykloheptendikarbonylovou group.

-5GB 289892 B6

When R ² is a trivalent radical of a tricarboxylic acid is typically the radical trimellitylovou or nitrilotriacetylovou.

When R ² is a tetravalent radical of a tetracarboxylic acid is typically the tetravalent radical of butane-l, 2,3,4-tetracarboxylic acid or of pyromellitic acid.

When R ² is a divalent radical of a dicarbamic acid is typically hexamethylendikarbamoylovou or 2,4-tolylendikarbamoylovou group.

Examples of polyalkylpiperidine compounds of this group include the following:

1) 4-hydroxy-2,2,6,6-tetramethylpiperidine

2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

4) 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine

5) 4-stearyloxy-2,2,6,6-tetramethylpiperidine

6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine

7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine

8) 1,2,2,6,6-Pentamethylpiperidin-4-yl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

9) di (1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate

10) di (2,2,6,6-tetramethylpiperidin-4-yl) succinate

11) di (2,2,6,6-tetramethylpiperidin-4-yl) glutarate

12) di (2,2,6,6-tetramethylpiperidin-4-yl) adipate

13) di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate

14) di (1,2,6,6-pentamethylpiperidin-4-yl) sebacate

15) di (1,2,3,4,6-tetramethyl-2,6-diethylpiperidin-4-yl) sebacate

16) di (1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate

17) 1-propargyl-4 H -cyanethyloxy-2,2,6,6-tetramethylpiperidine

18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate

19) tri (2,2,6,6-tetramethylpiperidin-4-yl-trimellitate)

20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine

21) di (2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate

22) di (1,2,2,6,6-pentamethylpiperidin-4-yl) dibutyl malonate

-6GB 289892 B6

23) butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonate di (1,2,2,6,6-pentamethylpiperidin-4-yl) ester

24) di (1,2,2,6,6-Pentamethylpiperidin-4-yl) dibenzyl malonate

25) di (1,2,3,6-tetramethyl-2,6-diethylpiperidin-4-yl) dibenzyl malonate

26) hexane-1 ', 6-bis (4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)

27) Toluene-2 ', 4'-bis (4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)

28) dimethylbis (2,2,6,6-tetramethylpiperidin-4-oxy) silane

29) phenyltris (2,2,6,6-tetramethylpiperidin-4-oxy) silane

30) tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite

31) tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate

32) phenylbis (1,2,2,6,6-pentamethylpiperidin-4-yl) phosphonate

33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine

34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine

35) 4-hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine

36) N-hydroxy-2,2,6,6-tetramethylpiperidine 1-carbohydrates

b) Compounds of general formula ΙΠ

where n is 1 or 2,

R ¹ is as defined under a),

R ³ is hydrogen, C 1 -C 12 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 2 -C 18 alkanoyl , C3 -C5 alkenoyl or benzoyl,

R ⁴ is, when n is 1, hydrogen, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl substituted by hydroxyl cyano, alkoxycarbonyl or carbamido, glycidyl, or -CH 2 -CH (OH) -Z or -CONH-Z, wherein:

Z represents a hydrogen atom, a methyl group or a phenyl group, if n is 2, R ⁴ represents a C 2 -C 12 alkylene group, a C 6 -C 12 arylene group, a xylylene group, a group of the formula -CH 2 -CH (OH) -CH ₂ or a group of the formula -CH 2 -CH (OH) -CH ₂ -ODO-, wherein

D represents an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to 15 carbon atoms or a cycloalkylene group having 6 to 12 carbon atoms, or provided that R ³ represents an alkanoyl group, an alkenoyl group or a benzoyl group, R ⁴ may represent also a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or also a group -CO-, or R ³ and R ⁴ together, if n is 1, may be a divalent radical of aliphatic, cycloaliphatic or aromatic 1,2- or 1, 3-dicarboxylic acids.

When any substituents are alkyl of 1 to 12 carbon atoms or 1 to 18 carbon atoms, they are as defined in (a) above.

When any substituents are C 5 -C 7 cycloalkyl, they are in particular cyclohexyl.

In the meaning of the C 7 -C 8 aralkyl group, R ^{3 is} especially phenylethyl or especially benzyl. In the meaning of the C 2 -C 5 hydroxyalkyl group, R ^{3 is} especially 2-hydroxyethyl or 2-hydroxypropyl.

The symbol R @ ³ in the meaning of alkanoyl groups having 2 to 18 carbon atoms is for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, but preferably acetyl, and in the meaning alkenoyl group with 3-5 carbon atoms, in particular acryloyl.

When R ^{@ 4} represents a C2 -C8 alkenyl group, it is, for example, allyl, methylallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

R ⁴ as hydroxy, cyano, alkoxycarbonyl or carbamido substituted C 1 -C 4 alkyl may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylethylamine or 2- (aminocarbonylethyl) or 2- (aminocarbonylethyl) ) ethyl group.

When any substituents are C 2 -C 12 alkylene, they are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

When any substituents are a C 6 -C 15 arylene group, they are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

-8EN 289892 B6

C 6 -C 12 cycloalkylene denotes in particular cyclohexylene.

Examples of polyalkylpiperidine compounds of this group include the following:

37) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine

38) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diacetamide

39) 1-acetyl-4- (N-cyclohexylacetamido) -2,2,6,6-tetramethylpiperidine

40) 4-Benzoylamino-2,2,6,6-tetramethylpiperidine

41) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dibutyl adipamide

42) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dicyclohexyl-2-hydroxypropylene-1,3-diamine

43) N, N'-bis (2,2,6,6-tetraineethylpiperidin-4-yl) -p-xylylenediamine

44) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) succinamide

45) di (2,2,6,6-tetramethylpiperidin-4-yl) -N-2,2,6,6-tetramethylpiperidin-4-yl-β-aminodipropionate

46) a compound of formula

47) 4- (bis-2-hydroxyethylamino) -1,2,2,6,6-pentamethylpiperidine

48) 4- (3-methyl-4-hydroxy-5-tert-butylbenzamido) -2,2,6,6-tetramethylpiperidine

49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine

-9EN 289892 B6 (IV)

c) Compounds of formula IV

wherein n is 1 or 2

R ¹ is as defined under a), and

R ⁵ denotes, if n is 1, an alkylene group having 2 to 8 carbon atoms, a hydroxyalkylene group having 2 to 8 carbon atoms or an acyloxyalkylene group having 4 to 22 carbon atoms, and if n is 2, R ^{5 is a} group of formula ( -CH ₂ ) ₂ C (CH ₂ -) ₂ .

When R ⁵ represents an alkylene or hydroxyalkylene group having 2 to 8 carbon atoms, it represents, for example, an ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene group.

In the meaning of the C 4 -C 22 acyloxyalkylene group, R ^{5 is,} for example, a 2-ethyl-2-acetoxymethylpropylene group.

Examples of polyalkylpiperidine compounds of this group include the following:

50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane

51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro [5.5] undecane

52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro [4.5] decane

53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] undecane

54) 9-Aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane

55) 2,2,6,6-tetramethylpiperidine-4-spiro-2 '- (1', 3'-dioxane) -5'-spiro-5- (1,3-dioxane) -2spiro-4 '' ' - (2 '', 2 ', 6', 6'-tetramethylpiperidine)

-10GB 289892 B6 (VA)

d) Compounds of formulas VA, VB and VC

O - C - T ₂

N - C = O and ₃ H

CHj (UK)

(VC) in which n is the number 1 or 2,

R ¹ is as defined under a),

R ⁶ represents a hydrogen atom, a C 1 -C 12 alkyl group, an allyl group, a benzyl group, a glycidyl group or a C 2 -C 6 alkoxyalkyl group, and

R ⁷ is, when n is 1, hydrogen, C 1 -C 12 alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, hydroxyalkyl (C 2 -C 4) group, (C 2 -C 6) alkoxyalkyl, (C 6 -C 10) aryl group, glycidyl group, or - (CH ₂ ) p -COO-Q or - (CH ₂ ) _P- O-CO-Q, wherein p is 1 or 2 a

Q is C 1 -C 4 alkyl or phenyl, when n is 2, R ⁷ is C 2 -C 12 alkylene, C 4 -C 12 alkenyl, C 6 -C 12 arylene, a group of the formula -CH ₂ -CH (OH) -CH ₂ -ODO-CH ₂ -CH (OH) -CH ₂ -, wherein

-11 GB 289892 B6

D represents an alkylene group having 2 to 10 carbon atoms, an arylene group having 6 to carbon atoms or a cycloalkylene group having 6 to 12 carbon atoms, or a group of the formula -CH ₂ CH (OZ ') CH ₂ - (OCH 2 -CH (OZ')) CH 2) 2 -, where

Z 'is hydrogen, C 1 -C 18 alkyl, allyl, benzyl, C 2 -C 12 alkanoyl or benzoyl, and

Tj and T ₂ independently represent a hydrogen atom, an alkyl group having 1 to 18 or an unsubstituted or halogen or alkyl having 1 to 4 carbon atoms substituted by aryl having 6 to 10 carbon atoms or aralkyl of 7 to 9 carbon atoms, or

T ₁ and T ₂ together with the carbon atom to which they are attached form a C 5 -C 12 cycloalkane ring.

When any substituents are C 1 -C 12 alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl , n-decyl, n-undecyl or n-dodecyl.

Any substituents within the meaning of an alkyl group having 1 to 18 carbon atoms may represent, for example, the abovementioned groups and additionally, for example, an n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl group.

When any substituents are C 2 -C 6 alkoxyalkyl, they are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

When R ⁷ represents a C 3 -C 5 alkenyl group, it is, for example,

A 1-propenyl, allyl, methylallyl, 2-butenyl or 2-pentenyl group.

In the meaning of the C 7 -C 9 aralkyl group, R ⁷ , T 1 and T 2 are especially phenyl or especially benzyl. When T ₁ and T ₂ together with the carbon atom form a cycloalkane ring, it may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

When R ⁷ represents a C 2 -C 4 hydroxyalkyl group, it represents, for example

2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

In the term C 6 -C 10 aryl, R ⁷ , Ti and T _{2 are} especially phenyl, α- or β-naphthyl, which are unsubstituted or substituted by halogen or C 1 -C 4 alkyl.

When R ⁷ represents a C 2 -C 12 alkylene group it is, for example, an ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene group.

In the meaning of the C 4 -C 12 alkenyl group, R ^{7 is} especially a 2-butenylene, 2-pentenylene or 3-hexenylene group.

-12GB 289892 B6

When R ⁷ is a C 6 -C 12 arylene group, it is, for example, o- or p-phenylene, 1,4-naphthylene or 4'-biphenylene.

When Z 'is C 2 -C 12 alkanoyl, it is, for example, propionyl, butyryl, octanoyl or dodecanoyl, but preferably acetyl.

(C 2 -C 10) alkylene, (C 6 -C 15) alkylene or (C 6 -C 12) cycloalkylene group (D) as defined in (b).

Examples of polyalkylpiperidine compounds of this group include the following:

56) 3-Benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4,5] -decane-2,4-dione

57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4,5] -decane-2,4-dione

58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro [4,5] -decane-2,4-dione

59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro [4,5] decane-2,4-dione

60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione

61) 2-Isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4.5] decane

62) 2,2-Dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane

63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro [5,1,11,2] heneicosan

64) 2-Butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro [4,5] decane

65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5] decane-2,4-don

Or compounds of the following formulas

66)

CH, CH,

NH-C = O ch ₃ -n 'Yi - N - CH ₂ CH (OH) CH ₂ - (OCH 2 -CH (OH) CH ₂ 1 ch ₃ ^{/ X} ch ₃ O

e) Compounds of formula VI

(VI) wherein n is the number 1 or 2,

R ⁸ represents a group of the general formula

- 14GB 289892 B6

where

R ¹ is as defined under a),

E represents an oxygen atom or a group -NR ¹¹ -,

A represents a (C 2 -C 6) alkylene group or - (CH ₂ ) 3 -O-, and x is 0 or 1

R ⁹ has the same meaning as R ⁸ or is one of the groups -NR ⁿ R ^12, -OR ^13, -NHCH2OR ¹³ or -N (CH 2 OR ^I3) _2,

R ¹⁰ when n is 1, has the same meaning as R ⁸ or R ⁹ , and when n is 2, is -EBE-, where

B represents a (C 2 -C 6) alkylene group which is not interrupted or is interrupted by -N (R **) -,

R ¹¹ represents a C 1 -C 12 alkyl group, a cyclohexyl group, a benzyl group or a C 1 -C 4 hydroxyalkyl group, or a group of the formula

R ¹² is C 1 -C 12 alkyl, cyclohexyl, benzyl or C 1 -C 4 hydroxyalkyl, and

R ¹³ is hydrogen, C 1 -C 12 alkyl or phenyl, or R ¹¹ and R ¹² together represent C 4 -C 5 alkylene or C 4 -C 5 oxaalkylene,

For example, a group of the formula

-CHgCHg

-CH ₂ CH ₂

or a group of formula

-CH ₂ CH ₂ _ / or also R ¹¹ and R ¹² are each a group of formula

When any substituents are C1 -C12 alkyl, they are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl , 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

When any substituents are C 1 -C 4 hydroxyalkyl, they are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

When A is C2 -C6 alkylene, it is, for example, ethylene, propylene, 2,2-dimethypropylene, tetramethylene or hexamethylene.

When R ^and R ¹² together represent alkylene with 4-5 carbon atoms or oxaalkylene with 4-4 carbon atoms, are for example tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds of this group include compounds of the following formulas:

-16GB 289892 B6

70)

(CH ₃ CH ₂ ) ₂ N

NfCH 3 CH 2

71)

N (C ₄ H ₉ ) ₂

72)

73)

-17GB 289892 B6

r-18GB 289892 B6

75) where R

R R

R-NH- _{(CH2) 3} -N - (CH ^ N --- _{(CH2) 3} -NH-R

76) wherein R j

R R

I I

R-NH- (CH ₂ ) ₃ -N- (CH ₂ ) ₂ -N- (CH ₂ ) ₃ -NH-R

77) ch ₃ yy

I I I

RN - {CH ₂ ) ₃ - N - (CH ₂ ) ₂ - (N 2) 3 '

CH ₃

AND

N --- R

-19GB 289892 B6 where R j

(78)

79)

N-C, H

HO-CH ₂ CH ₂ -N

CH ₃ CH ₃

N-CH ₂ CH ₂ -OH

-20GB 289892 B6

(80)

f) Oligomeric or polymeric compounds whose repeating structural units contain one or more 2,2,6,6-tetraalkylpiperidine radicals of the formula I, in particular polyesters, poly5 ethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates , polysiloxanes, poly (meth) acrylamides, and copolymers thereof containing such residues.

Examples of the 2,2,6,6-polyalkylpiperidine light stabilizers of this group 10 include compounds of the following formulas wherein m is a number from 2 to about 200.

81)

-21 GB 289892 B6

82)

CH ₃ CH, \ z ch ₃ λ X ch ₃ —FCH 3 -CHg-N 0- in II -C- (CH2) ₄ - -Lo < 1 H-N-CH 2 -CH 5 -O- C- (CH 3) ₄ - c -3- ch /

-22EN 289892 B6

87)

89)

C ₂ H ₅

I c --- I c ₂ h ₅ o II co

90)

-23EN 289892 B6

-24GB 289892 B6

95)

96)

N (R) C ₄ H ₉

or hydrogen

H ₉ C ₄ (R) N

N (R) C ₄ H ₉

where R is

N (R) C ₄ H ₉

-25GB 289892 B6

Of these, e) and f) are particularly suitable, in particular those tetraalkylpiperidine compounds which contain s-triazine groups. Furthermore, compounds 74, 76, 84, 87.92 and 95 are particularly suitable.

The amount of sterically hindered amine, preferably the tetramethylpiperidine compound, depends on the intended use of the plastic additive granules. These granules expediently contain 0 to 90% by weight, preferably 20 to 70% by weight, of a spherically hindered amine.

Antioxidants of the spherically hindered phenol type are generally known as antioxidants for organic materials and are often used to stabilize polymers. These compounds preferably contain at least one group of the general formula X

(X) in which

R 'represents a hydrogen atom, a methyl group or a tert-butyl group, and

R 'is unsubstituted or substituted alkyl or substituted alkylthioalkyl.

Particularly preferred are compounds which contain at least one group of formula X

(X) in which

R 1 represents a methyl or tert-butyl group, and

R is unsubstituted or substituted alkyl or substituted alkylthioalkyl.

Examples of such phenolic antioxidants include:

1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4- n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol,

2,6-dioctadecyl-4-methylphenyl, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylpheno, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (r) -methyl-1-undecyl) phenol, 2,4-dimethyl-6- (1-methyl-1'-heptadecyl) phenol, 2,4-dimethyl-6- (1'-methyl-1'-tridecyl) phenol, and mixtures thereof .

-26GB 289892 B6

2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-1-methoxyphenol;

2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,

2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, bis (3,5-di-tert-butyl). butyl-4-hydroxyphenyl) adipate.

4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4-thiobis (6-tert-butyl-3- methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-disecamylphenol), 4,4'-bis (2,6-dimethyl- 4-hydroxyphenyl) disulfide.

6. Alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl -6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis- ( 4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [ 6- (α-methylbenzyl) -4-nonylphenol], 4,4'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol) 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyl) butane, 2,6-bis (3- tert-butyl 1-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis ( 5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3- tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'hyd) Roxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl) 4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4- hydroxy-2-methylphenyl) pentane.

7. Ο-, N- and S-benzyl compounds, for example 3,5,3 ', 5'-tetrater-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris (3) 5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3 5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate, di [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5- di-tert-butyl-4-hydroxybenzyl) malonate.

9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl- 4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

10. Triazine compounds, for example 2,4-bisoctylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5- di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4, 6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy)

289892 B6 phenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

11. Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-

3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium monoethyl-3,5- di-tert-butyl-4-hydroxybenzylphosphonate.

12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-tert-butyl-4-hydroxyphenyl) carbamate.

13. 3- (3,5-Di-tert-butyl-4-hydroxyphenyl) -propionic acid esters of monovalent or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol,

1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) 3-triaundeclamide 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7trioxabicyclo [2.2.2] octane.

14. 3- (5-tert-Butyl-4-hydroxy-3-methylphenyl) -propionic acid esters of monovalent or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol,

1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, N-tris (hydroxyethyl) bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

15. Esters of p- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with univalent or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol,

1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propandil, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'_bis (hydroxyethyl) oxalamide, 3 3-thiapentadecanol, trimethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monovalent or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol , neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylhexanediol, trimethylhexanediol. 6,7-trioxabicyclo [2.2.2] octane.

17. Amides | F (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

Preference is given to the antioxidants mentioned above under points 7,9, 10, 13, 14, 15 and 17, in particular under points 7, 9, 10 and 13, in particular octadecanol ester and β- (3,5-di-tert-butyl-4-). hydroxyphenyl) propionic acid and tetrakis [3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane. Most preferred is tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane.

-28GB 289892 B6

Other particularly preferred compounds are:

AO-004

O

{2- (1,1-dimethylethyl) -6-3- (1,1-dimethylethyl) -2-hydroxy-5-methylphenyl] methyl] -4-methylphenyl-2-propenoate}

{1,6-hexanediyl-3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl propanoate}

-29GB 289892 B6 (AO-006)

{1,2-ethanediylbis (oxy-2,1-ethanediyl) -3- (1,1-dimethylethyl) -4-hydroxy-5-methylphenylpropanoate} (AO-007)

ch ₂ sc ₃ h ₁₇ {2-Methyl-4,6-di [(octylthio) methyl] phenol} (AO-008)

{2,2'-Ethylidenebis (4,6-di-tert-butylphenol)} (AO-009)

O

CH ₂ CH ₂ COCH 2 CH ₂ {thiodi-2, l-ethanediyl-bis-3,5-di (1,1-dimethylethyl) -4-hydroxyfenylpropanoát}

-30GB 289892 B6 (AO-010)

OH

[4,4 ', 4' '- [(2,4,6-trimethyl-1,3,5-phenyltriyl) tris- (methylene)] tris [2,6-bis (1,1-dimethylethyl) phenol) AO-Oll

OH

{1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) trion)

-31 GB 289892 B6

The amount of antioxidants of the sterically hindered phenol type depends on the intended use of the plastic additive granules. These granules expediently contain 0 to 90% by weight, preferably 3 to 60% by weight, of antioxidants of the sterically hindered phenol type.

Organic phosphites and phosphonites are also known as stabilizers for plastics. They are used in particular as processing stabilizers for polyolefins.

These are predominantly aromatic phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (diphenyl alkyl phosphite) amines, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythrityldiphosphite, tri- (diphenyl diphenyl phosphite), 2,4-di-tert-butylphenyl) -pentaerythrityl diphosphite, tristaerylsorbityl triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, 3,9-bis (2,4-di-tert-butyl-4-methylphenoxy) - 2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane, 3,9-tris (2,4,6-tris-tert-butylphenoxy) 2,4,8,10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane; and 2,2'-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite.

Particularly preferred are the following phosphites:

(P-001) Tris (2,4-di-tert-butylphenyl) phosphite (P-002) (P-003)

-32GB 289892 B6 (P-004)

(P-006) (P-006)

P-007

(P-008) o-ch ₂ ch ₂ o / Ί '\

H ₃₇ -C _le OP / o — ch ₂ ch ₂ o

-33GB 289892 B6 (P-009)

Particularly preferred is tris (2,4-di-tert-butylphenyl) phosphite.

The amount of phosphite or phosphonite depends on the intended use of the plastic additive granules. These granules expediently contain 0 to 90% by weight, preferably 3 to 70% by weight, of phosphites or phosphonites.

In addition to sterically hindered phenol, the additive granules preferably also contain organic phosphite or phosphonite. Preferred are combinations of the preferred sterically hindered phenol and the preferred organic phosphites or phosphonites as mentioned above, for example, a combination of an octanol or octadecanol ester and P- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid or tetrakis [3 (3, 5-di-tert-butylhydroxyphenyl) propionyloxymethyl] methanustris (2,4-di-tert-butylphenyl) phosphite. Most preferred is a combination of tetrakis [3- (3,5-di-tert-butylhydroxyphenyl) propionyloxymethyl] methane and yt (2,4-di-tert-butylphenyl) phosphite. The weight ratio between sterically hindered phenol and aphosphite or phosphonite is preferably from 20: 1 to 1:20, particularly preferably from 10: 1 to 1:10, and particularly preferably from 4: 1 to 1: 4.

The compounds of the group comprising hydrotalcites, metal carbonates and metal oxides which can be used according to the invention are both naturally occurring minerals and synthetic compounds.

Compounds of the hydrotalcite family may be represented by the general formula X

M ²⁺ i_x.M ³ \. (OH) 2 (A ^n-) _{x / n} MH @ ₂ O (X) wherein

M ²⁺ is Mg ^2+, Ca ^2+, Sr ²⁺ \ Ba ^2+, Zn ^2+, Cd ^2+, Pb ^2+, Sn ²⁺ and / or Ni ²⁺

M ³⁺ means Al ³⁺ , B ³⁺ , or Bi ³⁺ ,

A represents an anion with a valency of n, n is a number from one to four, x is a number from 0 to 0.5, and m is a number from 0 to 2.

A 'is preferably OH, Cl, Br, Γ, C10 ₄ , HCO ₃ , CH ₃ COO, C ₆ H ₅ COO, CO ₃ ² ', SO ^{4 2} ', COO, (CHOHCOO) 2 ² ·, (CHOH) ₄ CH ₂ OHCOO,

AND

COO

-34GB 289892 B6

C ₂ H 4 (COO) ₂ ² ', (CH 2 COO) 2 ^2-, CHjCHOHCOCF, SiO3 ^2', could., ^4; Fe (CN) 6 ³ ', Fe (CN) 6 ² or

HPO ₄ ² '.

Other hydrotalcites useful in the process described above are compounds of formula (Xa)

M 2 Al ₂ (OH) _{2X +} UAO ₂ .mH ₂ O (Xa) wherein in the above general formula Xa

M ²⁺ represents at least one metal selected from the group consisting of magnesium and zinc, and is preferably Mg ²⁺ , coo

A represents an anion, for example selected from the group consisting of CO ₃ , 1 COO / OH and S ² , wherein n denotes the anion valency, m represents a positive number, preferably from 0.5 to 5, and x represents positive numbers, x preferably having a value of 2 up to 6 and z is less than 2.

Preferred and commercially available hydrotalcites are DHT-4A and DHT-4C from Kyowa, Japan.

Preferred are compounds from the group of hydrotalcites of formula X

M ²⁺ 1_x.M ³⁺ x. (OH) _2. (A ^, nx _{/ n.} M H ₂ O (X) in which

M ²⁺ represents Mg ²⁺ or a solid solution of magnesium and zinc,

A 'is an anion of CO ₃ ^2- , x is a number from 0 to 0.5, and m is a number from 0 to 2.

Particularly preferred are the hydrotalcites of the formulas:

Al ₂ O ₃ .6MgO.CO ₂ .12H ₂ O

MG4, ₅ Al ₂ (OH) ₁₃ .CO ₃ .3,5H ₂ O

4MgO.Al ₂ O ₃ .CO ₂ .9H ₂ O

4MgO.Al ₂ O ₃ .CO ₂ .6H ₂ O

ZnO.3MgO.Al ₂ O ₃ .CO ₂ .8-9H ₂ O, or ZnO.3MgO.Al ₂ O ₃ .CO ₂ .5-6H ₂ O.

The amount of hydrotalcites depends on the intended use of the plastic additive granules. These granules expediently contain 0 to 50% by weight, preferably 3 to 40% by weight, of hydrotalcites.

Preferred metal oxides are divalent metal oxides. Particularly preferred are the metal oxides of the second main group or subgroup, with zinc oxide and magnesium oxide being particularly preferred.

The amount of metal oxide depends on the intended use of the plastic additive granules. These granules expediently contain 0 to 90% by weight, preferably 5 to 60% by weight, of metal oxide.

-35GB 289892 B6

Preferred metal carbonates are divalent metal carbonates. Particularly preferred are the metal carbonates of the second main group or the subgroup, with calcium carbonate being particularly preferred.

The amount of metal carbonate depends on the intended use of the plastic additive granules. These granules expediently contain 0 to 90% by weight, preferably 5 to 60% by weight, of a metal carbonate.

Another metal soap for the purposes of the invention is a metal salt of a fatty acid (with the exception of calcium stearate), wherein the metal may in particular be an element of the second major group or a minor group, or tin.

In particular, they are magnesium, tin, or preferably zinc salts selected from the group consisting of aliphatic saturated carboxylates of 2 to 22 carbon atoms, aliphatic olefinic carboxylates of 3 to 22 carbon atoms, aliphatic carboxylates of 2 to 22 carbon atoms substituted with at least one hydroxyl group, cyclic or bicyclic carboxylates of 5 to 22 carbon atoms, aromatic carboxylates of 7 to 22 carbon atoms, aromatic carboxylates of 7 to 22 carbon atoms substituted with at least one hydroxyl group, alkyl group of 1 to 16 carbon atoms substituted with phenylcarboxylates and phenylalkyl carboxylates of 1 to 16 carbon atoms in the alkyl moiety, with stearates, laurates and behenates being preferred. Other metal soaps are particularly preferably zinc stearate or magnesium stearate.

The amount of other metal soaps depends on the intended use of the plastic additive granules. These granules expediently contain 0 to 90% by weight, preferably 5 to 60% by weight, of another metal soap.

Preferred thioesters are esters of β-thiodipropionic acid, for example its lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide disodium pentaerythride, pentaerythrole;

Examples of suitable lubricants include ozokerite (montan wax), fatty acid esters, polyethylene waxes, amide waxes, chlorinated paraffins, glycerol esters or alkaline earth metal soaps. Suitable lubricants are also described in "Plastics Additives" by H. Gachter and H. Müller, Hanser Verlag, Third Edition, 1990, pp. 423-480.

The additive granules may further comprise compounds of Groups 2-10 below:

2. UV absorbers and light stabilizers

2.1. 2- (2'-hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5' tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert-butyl) 12'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl) -2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5 ' -bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, a mixture of 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-) 5 '- (2-ok 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hyeroxy- 5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenyl) benzotriazole, 2,2'-methylenebis [4 (1,1) , 3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol], the transesterification product of 2- [3'-tert-butyl 1-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol

-36GB 289892 B6

300, a compound of formula [R-CH 2 CH 2 -COCXCF 4 h, wherein R represents a 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl group.

2.2. 2-hydroxybenzophenones, for example, 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-4-dodecyloxy, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4,4 2-hydroxybenzophenone derivatives.

2.3. Esters of unsubstituted or substituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl -3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butyl butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acylates, for example ethyl-α-cyano-β, β-diphenylacrylate, isooctyl-α-cyano-β, (3-diphenylacrylate, methyl α-methoxycarbonylcinnamate, methyl α-cyano-p-methyl-β-methoxycinnamate, butyl) -cyano-4-methyl-p-methoxycinnamate, methyl-α-methoxycarbonyl-p-methoxycinnamate, and N- (β-methoxycarbonyl-β-cyanvinyl) -2-methylindoline.

2.5. Nickel compounds, for example, nickel complexes with 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol] such as 1: 1 and 1: 2 complexes, or without other ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts with monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, e.g. nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without other ligands.

2.6. Oxalamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy -2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4 ' di-tert-butyloxanilide, and mixtures of ortho- and para-methoxy and ortho- and para-ethoxy-disubstituted oxanilides.

2.7. 2- (2-hydroxyphenyl) -1,3,5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -

1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine,

2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2 4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-dodecyloxyphenyl) -4-, 6-bis (2,4-dimethylphenyl) 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butoxypropoxy) phenyl] -4,6 -bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine.

3. Metal deactivators, for example Ν, Ν'-diphenyloxalamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) ) hydrazine,

3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalodihydrazide, oxanilide, isophthalodihydrazide, sebacobisphenylhydrazide, N, N'-diacetyl adipodihydrazide, N, N'-bissalicyloyloxalodihydrazide and N, N'-bissalicyloodihydrazide.

4. Peroxide-destroying compounds, for example β-thiodipropionic acid esters, for example its lauryl ester, stearyl ester, myristyl ester or tridecyl ester, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, p-dioctadecyl disulfide pacetadecyl disulfide, dioctadecyl disodecyl disulfide.

5. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

-37GB 289892 B6

6. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example zinc stearate, magnesium behenate, stearate magnesium, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate and tin pyrocatecholate.

7. Nucleating agents, for example 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid.

8. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.

9. Other additives such as plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents and blowing agents.

10. Benzofuranones and indolinones, such as those disclosed in US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052, US-A-5,252 643, DE-A-4,316,612, DE-A-4,316,622, DE-A-4,316,876, EP-A-0 589,839 or EP-A-0 591 102 or 3- [4- (2- acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [ 5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4 (acetoxy-3,5-dimethylphenyl) 5,7-di-tert-butylbenzofuran-2-one; 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one.

The granules of the invention are suitable for stabilizing organic polymers or plastics against thermal, oxidative or light-induced degradation. Examples of such polymers include, but are not limited to, the following polymers:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, poly-1-butene, poly-4-methyl-1-pentene, polyisoprene or polybutadiene, and polymers of cycloolefins, for example cyclopentene or norbomene, further polyethylene (optionally crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

The polyolefins, i.e. the polymers of the monoolefins exemplified in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared in various ways, in particular using the following processes:

a) free-radical polymerization (usually at high pressure and high temperature),

(b) catalytic polymerization using a catalyst that typically contains one or more of Group IVb, Vb, VIb, or VIII of the Periodic Table. These metals usually have one or more ligands, such as oxides, halides, alkoxides, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium tetrachloride, alumina or silica. The catalysts may be soluble or insoluble in the polymerization medium and may be active as such or other activators may be used, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyloxides or metal alkyloxanes, which metals are elements of groups Ia, IIa and IIa. and / or IIIa of the periodic table. These activators can be modified, for example, with other ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene catalysts or single site catalysts (SSCs).

-38GB 289892 B6

2. Mixtures of the polymers referred to in paragraph 1, for example mixtures of polypropylene with co-isobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-1-butene copolymers, copolymers of propylene and isobutylene, and 1-butene, copolymers of ethylene and hexene, copolymers of ethylene and methylpentene, copolymers of ethylene and heptene, copolymers of ethylene and octene, copolymers of propylene and butadiene, copolymers of isobutylene and isoprene, copolymers of ethylene and alkylacrylate, copolymers of ethylene and alkylmeth their copolymers with carbon monoxide or copolymers of ethylene acrylic acid and their salts (ionomers) and terpolymers of ethylene with propylene and diene, such as hexadiene, dicyclopentadiene or ethylidennorbomen, and mixtures of these copolymers and mixtures thereof with the polymers mentioned in paragraph 1, for example copolymers polypropylene - ethylene - propylene, LDPE - ethylene - vinyl acetate copolymers, LDPE - ethylene - acrylic acid copolymers, LLDPE - ethylene - vinyl acetate copolymers, LLDPE - ethylene - acrylic acid copolymers, and alternating or random polyalkylene - carbon monoxide copolymers, and mixtures thereof with other polymers, for example with polyamides.

4. Hydrocarbon resins (for example from C 5 -C 9 monomers), including hydrogenated modifications thereof (for example, adhesives for the preparation of adhesives) and mixtures of polyalkylenes and starch.

5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with pulps or acrylic derivatives, for example styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate, high impact strength mixtures of styrene-other polymer copolymers, such as polyacrylate, pulp polymer or ethylene-propylene-marrow terpolymer, and styrene block copolymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene copolymers or on polybutadiene-acrylonitrile, styrene and acrylonitrile (or methacrylonitrile) copolymers on polybutadiene, styrene, acrylonitrile and methylbutadiene and methyl maleic acid on polybutadiene, styrene, acrylonitrile and maleic acid anhydride or maleimide on polybutadiene, styrene and maleimide on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on terpolymers ethylene - propylene and styrene and styrene, -acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof with the copolymers mentioned in paragraph 6, for example mixtures of copolymers known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and copolymers of epichlorohydrin, in particular polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride polyvinyl fluoride, polyvinylidene fluoride, vinyl chloride - vinylidene chloride vinyl chloride - vinyl acetate or vinylidene chloride - vinyl acetate.

9. Polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles, the impact resistance of which is modified with butyl acrylate.

-39GB 289892 B6

10. Copolymers of the monomers referred to in paragraph 9 with or with other unsaturated monomers, for example copolymers of acrylonitrile and butadiene, acrylonitrile and alkyl acrylate, akiylonitrile and alkoxyalkyl acrylate or acrylonitrile and vinyl halide or terpolymers of acrylonitrile, alkyl and methacrylate.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl-melamine, and copolymers thereof with the olefins referred to in paragraph 1.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene as well as those polyoxymethylenes which contain comonomers, for example ethylene oxide, polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures thereof with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes and aliphatic or aromatic polyisocyanates, and precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or corresponding lactams, such as nylon 4, nylon 6, nylon 6/6, 6/10, 6/9, 6/12, 4/6 and 12/12, nylon 11, nylon 12, aromatic polyamides derived from m-xylene, diamine and adipic acid, polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally with an elastomer as modifying agent, for example poly-2,4,4 —Trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide, and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers, or with polyethers, for example polyethylene glycol, polypropylene glycol or polytetramethylene, modified EPDM or ABS, and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block polyether esters derived from hydroxyl-terminated polyethers as well as polyesters modified by polycarbonates or MBS.

19. Polycarbonate and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.

22. Drying and non-drying alkyd resins.

-40GB 289892 B6

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, as well as their low-flammable halogen-containing modifications.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins or acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example from bisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, natural rubber, gelatin, and derivatives thereof, which are chemically modified in a polymer homologous manner, such as cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methylcellulose, as well as natural resins and derivatives thereof.

Mixtures of the aforementioned polyblends, for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PP, PA / PPO.

29. Natural and synthetic organic substances which are pure monomeric compounds or mixtures of such compounds, such as mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (for example, phthalates, adipates, phosphates or trimellitates) and mixtures of synthetic esters with mineral oils in any weight ratios, for example mixtures used as spinning mixtures, as well as aqueous emulsions thereof.

30. Aqueous emulsions of natural or synthetic rubbers, for example natural rubber latex or latexes of carboxylated styrene-butadiene copolymers.

Accordingly, the invention further relates to compositions comprising an organic polymer susceptible to thermal, oxidative or light-induced degradation and granules of the invention. Surprisingly, the polymers stabilized by the granules according to the invention show a higher stability than the polymers stabilized by means of a conventional additive mixture. The granules-containing polymers of the invention may further comprise one or more conventional other plastic additives. These additives are preferably selected from the group consisting of sterically hindered amines (HALS), sterically hindered phenols, phosphites or phosphonites, hydrotalcites, metal oxides, metal carbonates, other metal soaps, antistatic agents, anti-sticking agents, flame retardants, thioesters, internal and external lubricants, pigments, UV absorbers and other light stabilizers. Preferred compounds (and their detailed description) are given for low-dust granules. The other plastic additive or additives may be in any conventional physical form, for example, in crystalline form, in powder, pellet, granular, dispersed or liquid form. The polymer may also contain more than one granulate according to the invention.

Preferred organic polymers are synthetic polymers and especially polymers of the above group 1, especially polyethylene and polypropylene.

The granules are expediently added to the organic polymers to be stabilized in amounts of from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight, based on the total weight of the organic polymer to be stabilized.

-41 CZ 289892 B6

The granules of the invention and any other additives may be incorporated into the organic polymer by known methods, for example before or during molding or by applying dissolved or dispersed granules to the polymer, if desired with subsequent solvent evaporation. These granules can also be used to produce so-called premixes.

A method of stabilizing an organic polymer comprising incorporating effective stabilizing amounts, as described above, of low dust granules into said polymer is another object of the invention. Preferred embodiments of low-dust granules are analogous to polymer.

Numerous forms can be made from such a stabilized polymer in a conventional manner, for example, foils, fibers, bands, molding compositions or profiles.

The invention is illustrated in more detail by the following examples, which are not intended to limit the scope of the invention in any way. In these examples, as in the rest of the specification, the parts are by weight and the percentages are by weight and the symbol "[denotes a tert-butyl residue." I "

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Calcium stearate powder (Radiastar 1060, FINA, Germany) is fed gravimetrically at 20 kg / h into a twin screw extruder (type DNDL44, Bohler, Switzerland) using a metering unit. The extruder is temperature controlled and has the following temperature diagram (profile): 18 ° C / 18 ° C / 200 ° C / 200 ° C / 230 ° C / 230 ° C / 230 ° C / 175 ° C / 175 ° C / 175 ° C. The nozzle temperature is 180 ° C. Gas extraction (steam removal) takes place in the fifth zone. The product is extruded through 8 nozzles with a diameter of 2 mm at a screw speed of 135 rpm. Immediately downstream of the nozzles, the plastic extrudates (10,000 to 100,000 Pa.s) were cut and then cooled to 30 ° C in a fluid bed cooler with air at 21 ° C.

The granules according to the invention obtained in this way are spherical and fairly regular in shape and exhibit favorable bulk material properties (see Table 1), particularly as compared to the powder used.

Table 1

granule powder particle size, shortest dimension ¹ > 1 mm <0.05 mm Part size, longest dimension ¹ 2-6 mm <0.1 mm bulk density 650 g / l 200 g / l creep time (tRl 5) ² 6,6 s * water content ³ 0.6% 3.1% dust release (5 min) ⁴ 0.08% > 1% angle of repose ⁵ 32 ° 52 °

Legend to Table 1:

¹ according to ISO 3435, ² according to DIN 53492, ³ determined by Karl Fischer method, ⁴ according to Heubach test, ⁵ according to ISO 4324, * not liquid

-42EN 289892 B6

Example 2 parts of calcium stearate powder (Radiastar 1060, FINA, Germany) and 30 parts of Irganox 1076 (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester, Ciba, Switzerland) are mixed homogeneously in a mixer (Loedige). The mixture is fed gravimetrically into the twin screw extruder (type DNDF93, Biihler, Switzerland) at a rate of 100 g / h using a metering unit. The extruder is temperature controlled and has the following temperature diagram (profile): 21 ° C / 205 ° C / 205 ° C / 205 ° C / 80 ° C / 80 ° C / 30 ° C / 15 ° C / 15 ° C / Low: 14 ° C. The nozzle temperature is 180 ° C. The product is extruded through 30 nozzles with a diameter of 2 mm at a screw speed of 45 rpm. Immediately downstream of the nozzles, the extrudates are cut in a plastic state and then cooled to 30 ° C in a fluid bed cooler with air at 21 ° C.

The granules according to the invention prepared in this way have a spherical and fairly regular shape and exhibit very favorable bulk material properties (see Table 2, granules 2).

Example 3 parts of calcium stearate powder (Radiastar 1060, FINA, Germany), 30 parts of Irganox 1010 (pentaerythrityl ester | N - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, Ciba, Switzerland) and 30 parts of Irgafos 168 (tris (2,4-di-tert-butylphenyl) phosphite, Ciba, Switzerland) was mixed homogeneously in a mixer (Loedige). The mixture is fed gravimetrically into the twin screw extruder (type DNDF93, Buhler, Switzerland) at a rate of 10 kg / h using a metering unit. The extruder is temperature controlled and has the following temperature diagram (profile): 21 ° C / 240 ° C / 240 ° C / 240 ° C / 220 ° C / 220 ° C / 200 ° C / 15 ° C / 15 ° C / Low: 14 ° C. The nozzle temperature is 150 ° C. The product is extruded through 8 nozzles with a diameter of 2 mm at a screw speed of 91 rpm. Immediately downstream of the nozzles, the plastic extrudates are cut and then cooled to 30 ° C in a fluid bed cooler with air at 21 ° C.

The granules according to the invention prepared in this way have a spherical and fairly regular shape and exhibit very favorable bulk material properties (see Table 2, granules 3).

Table 2

granules 2 granule 3 particle size, the shortest dimension ¹ > 1 mm > 1 mm particle size, the longest dimension of ¹ 2-4,5 mm 2-5 mm bulk density 545 g / l 580 g / l creep time (tR15) ² 9.9 s 8,5 s water content ³ 1.1% 1,8% dust release (5 min) ⁴ 0.02% 0,07% angle of repose ⁵ 40 ° 37 °

Legend to Table 2:

¹ according to ISO 3435 ² according to DIN 53492, ³ determined by Karl Fischer method and standardized to 100% calcium stearate, ⁴ according to Heubach test ⁵ according to ISO 4324,

-43GB 289892 B6

Example 4

1.5 g Irganox B 215 (pentaerythrityl ester of p- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and tris (2,4-di-tert-butylphenyl) phosphite 1: 2, Ciba, Switzerland) is mixed with 0.75 g of calcium stearate granules (prepared as described in Example 1) and 1500 g of polypropylene powder for 2 minutes in a water-cooled fluidic mixer. The comparative mixture was prepared analogously but containing 0.75 g of calcium stearate powder (Radiastar 1060, FINA, Germany).

Both blends are extruded five times in a screw extruder (20d) at a maximum temperature of 260 ° C. After the first, third and fifth extrusions, the melt flow index (MFI, at 230 ° C and 2.15 kg, according to ISO 1133) are determined, and in addition, after the fifth extrusion, the yellowness index (YI) on the pressed plates is determined. thickness 2 mm.

Table 3

mixture melt flow index after extrusion: yellowing index first third fifth the calcium stearate of Example 1 4.7 6.1 7.7 4.9 calcium stearate powder 5.0 6.6 8.5 5.7

The lower melt index and yellowing index values clearly indicate that better stabilization is achieved with the calcium stearate granules of the invention than with conventional calcium stearate powder.

Example 5

2.25 g of granules of the invention extruded at 180 ° C containing 22.2 parts of Irganox 1010 (pentaerythrityl ester 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, Ciba, Switzerland), 44.5 parts of Irgafos 168 (tris (2,4-di-tert-butylphenyl) phosphite, Ciba, Switzerland) and 33.3 parts of calcium stearate are mixed with 1500 g of polypropylene powder for 2 minutes in a water-cooled fluidic mixer.

The mixture is extruded five times in a screw extruder (20d) at a maximum temperature of 260 ° C. After the fifth extrusion, the yellowness index (YI) is determined on 2 mm thick pressed plates. The yellowness index obtained is 3.3.

Example 6

0.75 g of granules according to the invention extruded at 180 ° C containing 66.7 parts of Irganox 1010 (Penta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid pentaerythrityl ester, Ciba, Switzerland) and 33.3 parts of stearate calcium and 1.5 g granules of the invention extruded at 180 ° C containing 66.7 parts of Irgafos 168 (tris (2,4-di-tert-butylphenyl) phosphite, Ciba, Switzerland) and 33.3 parts of calcium stearate are mixed with 1500 g of polypropylene powder for 2 minutes in a water-cooled fluidic mixer.

The mixture is extruded five times in a screw extruder (20d) at a maximum temperature of 260 ° C. After the fifth extrusion, the yellowness index (YI) is determined on 2 mm thick pressed plates. The yellowness index obtained is 4.6.

-44GB 289892 B6

Example 7

1.125 g of granules of the invention extruded at 180 ° C containing 66.7 parts of Irganox 1010 (pentaerythrityl ester 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, Ciba, Switzerland) and 33.3 parts of calcium stearate and 1.125 g of granules of the invention extruded at 180 ° C containing 66.7 parts of Irgafos 168 (tris (2,4-di-tert-butylphenyl) phosphite, Ciba, Switzerland) and 33.3 parts of calcium stearate are mixed with 1500 g of polypropylene powder. for 2 minutes in a water-cooled fluidic mixer.

The mixture is extruded five times in a screw extruder (20d) at a maximum temperature of 260 ° C. After the fifth extrusion, the yellowness index (YI) is determined on 2 mm thick pressed plates. The yellowness index obtained is 4.8.

Example 8

1.5 g of Irganox B 215 (pentaerythrityl ester of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and tris (2,4-di-tert-butylphenyl) phosphite 1: 2, Ciba, Switzerland (extruded in the form of granules) is mixed with 0.75 g of calcium stearate granules (prepared as described in Example 1) and 1500 g of polypropylene powder for 2 minutes in a water-cooled fluidic mixer.

The mixture is extruded five times in a screw extruder (20d) at a maximum temperature of 260 ° C. After the fifth extrusion, the yellowness index (YI) is determined on 2 mm thick pressed plates. The yellowness index obtained is 4.7.

PATENT CLAIMS

Claims (26)

A low-dusting granule of plastic additives, characterized in that it contains at least 10 wt. calcium stearate, where the water content of the calcium stearate is less than 2% by weight, exhibits a particle size scattering, according to ISO 3435, from 1 to 10 mm, a bulk density greater than 400 g / l and a flowability tR25 nozzles according to DIN 53492, less than 15 s. The low-dust granules according to claim 1, characterized in that they comprise at least 20 wt. calcium stearate. The low-dust granules according to claim 2, characterized in that they contain at least 30 wt. calcium stearate. The low-dust granules according to claim 3, characterized in that they contain 100 wt. calcium stearate. The low-dust granules according to claim 1, characterized in that they have a particle size dispersion, according to ISO 3435, of from 1 to 6 mm. A low-powder granule according to claim 1, characterized in that the water content of the calcium stearate is less than 1% by weight. 7. The low-dust granules of claim 1, further comprising a compound selected from the group consisting of spherically hindered amines, spherically hindered phenols, -45EN 289892 B6 phosphites or phosphonites, hydrotalcites, metal oxides or carbonates, other metal soaps, antistatic agents, anti-sticking agents, flame retardants, thioesters, internal and external lubricants, pigments, UV absorbers and other light stabilizers or mixtures thereof. The low-powder granules of claim 1, further comprising a spherically hindered phenol and a phosphite or phosphonite. The low-dusting granule according to claim 8, wherein the steric hindered phenol is tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane and the phosphite is tris (2,4-di-tert-butylphenyl). ) phosphite. The low-dusting granule according to claim 9, wherein the weight ratio of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane to tris (2,4-di-tert-butylphenyl) phosphite is 20 : 1 to 1:20. The low-dusting granule according to claim 10, wherein the weight ratio of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane to tris (2,4-di-tert-butylphenyl) phosphite is 10 : 1 to 1: 10. A low-dust granule according to claim 11, wherein the weight ratio of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane to tris (2,4-di-tert-butylphenyl) phosphite is 4 : 1 to 1: 4. 13. The low-dust granules of claim 9, comprising about 40 parts by weight calcium stearate, about 30 parts by weight tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, and about 30 parts by weight. parts of tris (2,4-tert-butylphenyl) phosphite. 14. A process for the production of low-dusting plastic additive granules according to claim 1, characterized in that (a) heating a plastic additive mixture comprising at least 10 to 100% by weight of a plastic additive. % of calcium stearate, up to at least 80 wt. (b) extruding the resulting melt through a nozzle or aperture plate wherein the diameter of the thimble or aperture is from 1 to 10 mm, and (c) forming granules from the resulting extrudate while in plastic state. 15. The method of claim 14, wherein during said method a maximum temperature of said additive mixture of above 130 [deg.] C is reached. 16. The process according to claim 14, wherein during said process the maximum temperature of said additive mixture is reached above 150 [deg.] C. 17. The method of claim 14, further comprising aspirating gases from said melt. 18. The method of claim 14 wherein said additive mixture comprises calcium stearate, steric hindered phenol and phosphite or phosphonite. 19. The method of claim 18 wherein said additive mixture comprises calcium stearate, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, and tris (2,4-di-tert-butylphenyl). phosphite. -46GB 289892 B6 20. The method of claim 19 wherein the weight ratio of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane to tris (2,4-di-tert-butylphenyl) phosphite is from 20: 1 to 1: 20. 21. The process of claim 20 wherein the weight ratio of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane to tris (2,4-di-tert-butylphenyl) phosphite is from 10: 1 to 1: 10. 22. The process of claim 21 wherein the weight ratio of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane to tris (2,4-di-tert-butylphenyl) phosphite is 4: 1. to 1: 4. 23. The method of claim 19 wherein said additive mixture comprises about 40 parts by weight calcium stearate, about 30 parts by weight tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, and about 30 parts by weight. tris (2,4-di-tert-butylphenyl) phosphite. 24. A process for stabilizing an organic polymer, characterized in that the granules of claim 7 are incorporated into the polymer. 25. A composition comprising an organic polymer and additives, wherein the additives are in the form of granules according to claim 1. 26. The composition of claim 25 wherein the organic polymer is polyethylene or polypropylene.